New diol metabolites derived by biooxidation of chlorostyrenes with Pseudomonas putida: Determination of absolute stereochemistry and enantiomeric excess by convergent syntheses

Hudlický, Tomáš; Boros, Eric E.; Boros, Christie

doi:10.1016/s0957-4166(00)80247-5

Cited by 54 publications

(22 citation statements)

References 39 publications

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“…The cis-dihydrodiol bioproducts 2a -g were all found to be enantiopure ( > 98% ee) and compounds 2a, 2e -g showed the typical CD spectra associated with a (1S,2R) absolute configuration (l ¼ 218 -235 nm [De À ve], 280 -282 nm [De þ ve]); in accord with expectations from earlier biotransformations of monosubstituted and meta-disubstituted benzene substrates. The earlier report [14] of TDO-catalysed dihydroxylation (P. putida 39/D) of meta-chlorostyrene 1c to yield cis-dihydrodiol 2c with a lower enantiopurity value (1% yield, 54% ee), was not reproduced during this study using P. putida UV4.…”

Section: Resultscontrasting

confidence: 68%

“…[13 -15] It is noteworthy that in these examples the alkene was conjugated to an aryl group, e.g., oxidation of chlorostyrene 1c to yield arene-cis-dihydrodiol 2c and alkene-1,2-diol 3c (Scheme 1). [14] Similar studies have been reported on the dioxygenase-catalysed 1,2-dihydroxylation of the benzo-fused cyclic alkenes 6a -c to give the corresponding 1,2-diols…”

Section: Introductionmentioning

confidence: 56%

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Biocatalytic Asymmetric Dihydroxylation of Conjugated Mono‐ and Poly‐alkenes to Yield Enantiopure Cyclic cis‐Diols

et al. 2005

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Dioxygenase-catalysed asymmetric dihydroxylation, of a series of conjugated monoalkenes and polyenes, was found to yield the corresponding monols and 1,2-dihydrodiols. The diol metabolites were obtained from monosubstituted, gem-disubstituted, cis-disubstituted, and trisubstituted alkene substrates, using whole cells of Pseudomonas putida strains containing toluene and naphthalene dioxygenases. Dioxygenase selection and alkene type were established as important factors, in the preference for dioxygenase-catalysed 1,2-dihydroxylation of conjugated alkene or arene groups, and monohydroxylation at benzylic or allylic centres. Competition from allylic hydroxylation of methyl groups was observed only when naphthalene dioxygenase was used as biocatalyst. The structures, enantiomeric excess values and absolute configurations of the bioproducts, were determined by a combination of stereochemical correlation, spectroscopy (NMR and CD) and X-ray diffraction methods. cis-1,2-Diol metabolites from arenes, cyclic alkenes and dienes were generally observed to be enantiopure ( > 98% ee), while 1,2-diols from acyclic alkenes had lower enantiomeric excess values ( < 88% ee). The enantiopure cis-diol metabolite of a gem-disubstituted fulvene was used as precursor in a new chemoenzymatic route to a novel C 2 -symmetrical ketone.

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Section: Resultscontrasting

confidence: 68%

Section: Introductionmentioning

confidence: 56%

Biocatalytic Asymmetric Dihydroxylation of Conjugated Mono‐ and Poly‐alkenes to Yield Enantiopure Cyclic cis‐Diols

et al. 2005

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“…4, reaction B). P. putida 39/D also catalyzes the formation of a styrene cis-dihydrodiol (30), and Hudlicky et al observed changes in the regiospecificity and stereoselectivity of the toluene dioxygenase in this organism when chlorinated styrenes substituted at different ring positions were used as substrates (14). These results show that this family of dioxygenases catalyzes the dihydroxylation of -bond systems, with regioselectivity being determined by the position of the -bond.…”

mentioning

confidence: 58%

Stereospecific dihydroxylation of the styrene vinyl group by purified naphthalene dioxygenase from Pseudomonas sp. strain NCIB 9816-4

Lee

Gibson

1996

J Bacteriol

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Naphthalene dioxygenase (NDO) from Pseudomonas sp. strain NCIB 9816-4 adds both atoms of the dioxygen molecule to styrene to form (R)-1-phenyl-1,2-ethanediol. Product formation is tightly coupled to dioxygen consumption and NADH oxidation. NDO oxidizes styrene-d 8 at almost the same initial rate as styrene. The results indicate that dioxygen activation by NDO is different from that by cytochrome P-450 and other monooxygenases, which oxidize styrene to styrene 1,2-oxide.Bacterial dioxygenases which contain non-heme iron and Rieske-type (2Fe-2S) redox clusters play a crucial role in the initiation of the degradation of many aromatic hydrocarbons. These enzymes add both atoms of the dioxygen molecule to the aromatic ring of the substrate to form cis-dihydrodiols (10). One well-known example is the three-component naphthalene dioxygenase (NDO) from Pseudomonas sp. strain NCIB 9816-4 (6, 7, 11, 12, 26, 27), which catalyzes the homochiral dihydroxylation of naphthalene to (ϩ)-cis-(1R,2S)-dihydroxy-1,2-dihydronaphthalene (cis-naphthalene dihydrodiol) in the presence of dioxygen and NAD(P)H (15, 16) ( Fig. 1). Recent studies have shown that NDO exhibits a relaxed substrate specificity and catalyzes multiple oxidative reactions which lead to stereospecific monohydroxylation (9, 24, 31), desaturation (9, 23, 29), stereospecific sulfoxidation (18), O dealkylation (23), and N dealkylation (19) with appropriate substrates.Almost all of the reactions catalyzed by NDO are also catalyzed by cytochrome P-450 (hereafter called P-450). However, P-450 has not been reported to form cis-dihydrodiols and NDO has not been reported to form epoxides or catalyze National Institutes of Health shift reactions (5). We used styrene as a substrate for NDO to probe for epoxide formation, since P-450 monooxygenases are known to oxidize styrene to styrene 1,2-oxide (8, 34).Identification of reaction products. The oxidation of styrene by purified NDO components (reductase NAP , ferredoxin NAP , and ISP NAP ) (19, 28) was conducted in 2 ml of 50 mM sodium 2-(N-morpholino)ethanesulfonate (MES) buffer, pH 6.8, containing NADH (0.5 mol), Reductase NAP (16 g), Ferredoxin NAP (35 g), ISP NAP (50 g), Fe(NH 4 ) 2 (SO 4 ) 2 ⅐ 6H 2 O (0.1 mol), and styrene (0.25 mol). After 2 h, an internal standard (25 l of a 10 mM methanol stock solution of 1-phenethyl alcohol) was added to the reaction mixture, which was then extracted with ethyl acetate, concentrated, and analyzed by gas chromatography-mass spectrometry as described previously (24). Only one product, which eluted at 10.72 min and gave a mass spectrum identical to that given by authentic 1-phenyl-1,2-ethanediol, was detected. This product was purified by thin-layer chromatography (solvent, chloroform-acetone ϭ 8:2, R f ϭ 0.19), and its enantiomeric composition was determined by chiral stationary-phase-high-performance liquid chromatography (HPLC) on a Chiralcel OB-H column (4.6 mm by 25 cm, 5-m particle size; Chiral Technologies Inc., Exton, Pa.) (24). Enantiomers were eluted with hexane and 2-propanol ...

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“…gave, in addition to cis-dihydroarene diols, the diols (200) in a configuration dependent on the location of substitution (HUDLICKY et al, 1993;KONIGSBERGER and HUDLICKY, 1993). The sole example of dioxygenase-catalyzed oxidation of a non-aromatic substrate involves conversion of norbornadiene to the cis-exodiol (201) by Pseudomonas sp.…”

Section: Oxidation Of Styrenes By P Putida 391dmentioning

confidence: 99%

Hydroxylation and Dihydroxylation

Holland¹

2001

Biotechnology Set

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New diol metabolites derived by biooxidation of chlorostyrenes with Pseudomonas putida: Determination of absolute stereochemistry and enantiomeric excess by convergent syntheses

Cited by 54 publications

References 39 publications

Biocatalytic Asymmetric Dihydroxylation of Conjugated Mono‐ and Poly‐alkenes to Yield Enantiopure Cyclic cis‐Diols

Biocatalytic Asymmetric Dihydroxylation of Conjugated Mono‐ and Poly‐alkenes to Yield Enantiopure Cyclic cis‐Diols

Stereospecific dihydroxylation of the styrene vinyl group by purified naphthalene dioxygenase from Pseudomonas sp. strain NCIB 9816-4

Hydroxylation and Dihydroxylation

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